WO1996000227A1 - Preparation of triarylborane - Google Patents

Preparation of triarylborane Download PDF

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Publication number
WO1996000227A1
WO1996000227A1 PCT/US1995/007127 US9507127W WO9600227A1 WO 1996000227 A1 WO1996000227 A1 WO 1996000227A1 US 9507127 W US9507127 W US 9507127W WO 9600227 A1 WO9600227 A1 WO 9600227A1
Authority
WO
WIPO (PCT)
Prior art keywords
triarylborane
bph
adn
catalyst
phenyl
Prior art date
Application number
PCT/US1995/007127
Other languages
English (en)
French (fr)
Inventor
Albert Loren Casalnuovo
Thomas Foo
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to EP95922972A priority Critical patent/EP0766686B1/en
Priority to JP50317896A priority patent/JP3701677B2/ja
Priority to DE69502395T priority patent/DE69502395T2/de
Priority to MX9606723A priority patent/MX9606723A/es
Publication of WO1996000227A1 publication Critical patent/WO1996000227A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides

Definitions

  • This invention relates to the preparation of triarylborane from nickel complexes of the formula: Ni (NC(CH2) 4CN) 2 (NCBAr 3 ) 2 where Ar is phenyl or phenyl substituted with an alkyl group having 1 to 4 carbon atoms where the alkyl group may contain one or more fluorine atoms.
  • nickel complexes may be contained in catalytic residue formed during the alkene hydrocyanation (for example butadiene hydrocyanation) using organophosphorous nickel complexes as catalysts and triarylborane as catalytic promoters .
  • U.S. patent 3,798,256 discloses the hydrocyanation of 3-pentenenitrile to produce adiponitrile using nickel complexes as catalysts and organic boron compounds as promoters. Such hydrocyanation reactions produce catalyst residues which are primarily Ni (NCR) 4 (NCBAr 3 ) hereinafter referred to as NCBCs.
  • Shook U.S. Patent 4,082,811 discloses treating such residues with ammonium hydroxide to precipitate the amine adduct of triarylborane. The triarylborane can be recovered from the adduct by treatment with metal hydroxide--see Shook U.S. Patent 4,134,923.
  • the present invention is a direct method of recovery of the triarylborane promoter from the catalyst residue.
  • the present invention is a process for the manufacture of a triarylborane having the formula: BAr 3 where Ar is phenyl or phenyl substituted with an alkyl group having 1 to 4 carbon atoms where the alkyl group may contain one or more fluorine atoms, which comprises heating a complex of the formula: Ni (NC(CH ) 4CN) 2 (NCBAr 3 ) 2 where Ar is as above, in ar inert atmosphere at a pressure less than atmospheric to a temperature in the range of 120 degrees C to 300 degrees C; thus forming a vapor containing the triarylborane, and condensing triarylborane from the vapor.
  • an inert gas stream moves the vapor containing triarylborane to a zone where the triarylborane is condensed.
  • the drawing is a diagrammatic cross-sectional view of an apparatus suitable for use in carrying out the process of the invention.
  • the catalyst residue or NCBC is placed in a conventional sublimation apparatus and then heated under an inert atmosphere such as nitrogen or argon, or, preferably, under reduced pressure to decompose the catalyst residue or NCBC and release BAr 3 and RCN.
  • BAr 3 and RCN solidify on the sublimer cold finger. Temperatures ranging from 120°C to 300°C may be used, 170°C to 230°C is preferred. Pressures ranging from 0 to 760 torr may be used, .001 to 40 torr is preferred.
  • the catalyst residue or NCBC is placed in a tube and then heated, preferably under reduced pressure, while a stream of an inert carrier gas, such as nitrogen or argon, is passed over the catalyst residue or NCBC and through a cold trap.
  • an inert carrier gas such as nitrogen or argon
  • Ni catalysts of this type include Ni [P (OC 6 H 5 ) 3 ] 4 , Ni [ (0-p-C 6 H 4 CH 3 ) ] 4 , Ni [P (O-m- C 6 H 4 CH 3 ) 3 ]4, and Ni [P(0-m&p-C 6 H 4 CH 3 ) 3 ] .
  • the amount of promoter used can generally be varied from about 1:16 to 50:1 mole ratio of promoter to catalyst. A detailed description of the formation of catalyst residue is found in U . S . Patent 4 , 082 , 811 .
  • NCBC's can be prepared as described in Cone U.S. Pat. No. 4,394,321. Examples In the following examples, unless stated otherwise, all operations were carried out under a nitrogen atmosphere using a drybox or standard Schlenk techniques. Exposure of triphenylboron to air or moisture typically leads to the formation of diphenylboron derivatives.
  • ADN-NCBC refers to the NCBC derived from adiponitrile (ADN), specifically Ni (NC(CH 2 )4CN) 2 (NCBPh 3 ) 2 . Elemental analyses for the catalyst residue and ADN-NCBC were as follows. Ni Catalyst residue: C, 72.96; H, 5.66; N, 10.53. ADN-NCBC: C, 72.14; H, 5.70; N, 11.71; Ni, 6.56; B, 4.26.
  • Example 3 5.0 g of Ni catalyst residue was placed in a ceramic boat 1, inside a glass tube 2, as shown the figure. The pressure inside the system was reduced to about 20 torr while a nitrogen stream 4, was passed over the catalyst residue at a rate of about 200 ml/min. The tube was heated at 190°C for about 5 hours and the volatile products collected in the dry ice trap 3. 3.4 g of a pale yellow solid was collected from the trap. IH NMR spectroscopic analysis of the product indicated a mixture of BPh 3 and ADN that was 65% by weight BPh 3 . Hydrocyanation Performance Of BPh 3 Obtained from
  • Reaction rate 1.0 x 10 E-4 moles ADN / liter- second
  • the reactor was initially charged with a 3PN solution containing 24 wt.% Ni(TTP) 4 catalyst, 6.3 % TTP, and 0.28 % BPh 3 .
  • the steady-state conditions were achieved by pumping the following solutions in a continuous fashion for 41 hours:
  • the BPh 3 promoter solution was made with 52.0 g 3PN and 2.1 g of sublimed material, recovered from degraded Ni catalyst in the manner described in Example 2. Analysis of the solution by liquid chromatography showed that the solution contained 2.24 wt.% BPh 3 .
  • the reactor product was collected from the reactor overflow for analysis by gas chromatography.
  • the reaction of a given promoter can be characterized by the yields and selectivities shown below.
  • the results shown are averaged over samples taken at 17 to 41 hours from the inception of continuous flow. As a comparison, the results are also shown for a continuous hydrocyanation under the same conditions, except for the use of BPh3 purchased on the commercial market as the promoter. Recovered BPh 3 Purchased BPh3

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
PCT/US1995/007127 1994-06-23 1995-06-19 Preparation of triarylborane WO1996000227A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP95922972A EP0766686B1 (en) 1994-06-23 1995-06-19 Preparation of triarylborane
JP50317896A JP3701677B2 (ja) 1994-06-23 1995-06-19 トリアリールボランの製造
DE69502395T DE69502395T2 (de) 1994-06-23 1995-06-19 Herstellung von triarylboran
MX9606723A MX9606723A (es) 1994-06-23 1995-06-19 Preparacion de triarilborano.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/264,275 1994-06-23
US08/264,275 US5382697A (en) 1994-06-23 1994-06-23 Preparation of triarylborane

Publications (1)

Publication Number Publication Date
WO1996000227A1 true WO1996000227A1 (en) 1996-01-04

Family

ID=23005324

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/007127 WO1996000227A1 (en) 1994-06-23 1995-06-19 Preparation of triarylborane

Country Status (9)

Country Link
US (1) US5382697A (ja)
EP (1) EP0766686B1 (ja)
JP (1) JP3701677B2 (ja)
KR (1) KR100353777B1 (ja)
CN (1) CN1045445C (ja)
DE (1) DE69502395T2 (ja)
MX (1) MX9606723A (ja)
TW (1) TW320633B (ja)
WO (1) WO1996000227A1 (ja)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2849027B1 (fr) * 2002-12-23 2005-01-21 Rhodia Polyamide Intermediates Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques
FR2850966B1 (fr) 2003-02-10 2005-03-18 Rhodia Polyamide Intermediates Procede de fabrication de composes dinitriles
FR2854891B1 (fr) 2003-05-12 2006-07-07 Rhodia Polyamide Intermediates Procede de preparation de dinitriles
FR2854892B1 (fr) * 2003-05-12 2005-06-24 Rhodia Polyamide Intermediates Procede de fabrication de dinitriles
EP2395010B1 (en) * 2006-03-17 2016-07-13 Invista Technologies S.à.r.l. Method for the purification of triorganophosphites by treatment with a basic additive
US7709674B2 (en) * 2006-07-14 2010-05-04 Invista North America S.A R.L Hydrocyanation process with reduced yield losses
CN102241698B (zh) * 2011-05-23 2013-12-25 中国科学院理化技术研究所 星形三芳基硼烷类化合物及其制备方法和用途

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4134923A (en) * 1977-09-02 1979-01-16 E. I. Du Pont De Nemours And Company Process for producing a metal hydroxide adduct of a triarylborane
FR2518549A1 (fr) * 1981-12-21 1983-06-24 Du Pont Procede de recuperation de triarylboranes en solution dans des nitriles et procede de preparation de dinitriles le mettant en oeuvre

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798256A (en) * 1971-08-02 1974-03-19 Du Pont Hydrocyanation of olefins
US4082811A (en) * 1977-02-23 1978-04-04 E. I. Du Pont De Nemours And Company Recovery of metal and triarylborane catalyst components from olefin hydrocyanation residue
US4394321A (en) * 1981-11-12 1983-07-19 E. I. Du Pont De Nemours And Company Triarylboraneisocy ano metal compounds
US4749801A (en) * 1986-06-04 1988-06-07 E. I. Du Pont De Nemours And Company [Hexakis(pentenenitrilo)nickel II]bis-[μ-(cyano) bis(triphenylborane) (I)], its method of preparation and its use
US4847399A (en) * 1987-01-23 1989-07-11 Morton Thiokol, Inc. Process for preparing or purifying Group III-A organometallic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4134923A (en) * 1977-09-02 1979-01-16 E. I. Du Pont De Nemours And Company Process for producing a metal hydroxide adduct of a triarylborane
FR2518549A1 (fr) * 1981-12-21 1983-06-24 Du Pont Procede de recuperation de triarylboranes en solution dans des nitriles et procede de preparation de dinitriles le mettant en oeuvre

Also Published As

Publication number Publication date
KR100353777B1 (ko) 2003-01-06
JP3701677B2 (ja) 2005-10-05
US5382697A (en) 1995-01-17
MX9606723A (es) 1997-03-29
CN1045445C (zh) 1999-10-06
TW320633B (ja) 1997-11-21
EP0766686A1 (en) 1997-04-09
CN1151163A (zh) 1997-06-04
JPH10502080A (ja) 1998-02-24
DE69502395T2 (de) 1999-01-07
DE69502395D1 (de) 1998-06-10
EP0766686B1 (en) 1998-05-06

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